Synergistic insecticidal composition



s 101 29s sYNEncrsrrc rNsnicrfcmAr. coMrosirroN Mortimer T. Harvey,South Grange, N1, assignor to Harvel Research Corporation, a corporationoi New Jersey N Drawing. Filed Nov. 9, 1959, Ser. No. 851,551

r 9 Ciaims. (Q1. 167-24) The present invention relates to insecticidalcompositions comprising a main insecticide and an auxiliary materialwhich is a synergist for the main insecticide and which latter, in someof its examples, can act as a carrier base for the main insecticide,along with or without another base according to the relative solubilityof the main insecticide and the auxiliary material with respect to eachother.

.The said main insecticides used in the practice of the United StatesPatent 0 present invention are those materials known as rotenone androtenoids; pyrethnurn and the other pyrethrins; and the chlorinatedorganic compounds such as 2,2-bis-(p chlorphenyl)-1,l,1-trichloret hane,known as DDT and related materials; and 2,4 dichlorophenoxy acetic acidknown as 2,4-D; and the gamma isomer of hexachlorocyclohexane (known asLindane), dichlorodifluoromethane, (COI F and other chlorine fluorinederivatives of methane, andrelated materials.

The said other base can be deodorized kerosene (Deobase) and otherrefined petroleum oils tolerable to plants and animals and known aswhite oils, and as summer oils and foliage oils. For some purposes suchas those in which plant or animal tolerance are not necessary, petroleumoils in the less refined or even crude state can be used. Petroleum oilshave certaininsecti-cidal value and have other values in theinsecticidal field such as solvent characteristics, and low surfacetension and wetting characteristics. For some uses, such as in mosquitocontrol, crude petroleum oils are used alone but due to intolerance byplants and animals, including fish, the crude petroleum oils are notused. Refined petroleum oils,

however, are used in insecticides as solvents and bases for Iinsecticides of higher insecticidal values such as those of the rotenone(rotenoid) and pyrethrum (pyrethrin) classes and the chlorinatedhydrocarbon insecticides. However, due to the high cost of thepyrethrins, the comparative lower insecticidal value of the rotenoidsand the mammalian toxicity of the chlorinated organic compounds, it isdesirable to have a synergist for these insecticides to raise theirinsecticidal values.

I have discovered that hydrogenated condensation in which X representsradicals of the group Kl [le R is a radical of the group =G=O and o on3,101,296 1 Patented Aug. 20, 1963 "ice r 2 v and R is a hydrocarbon orcarbohydrate, modified or not modified with S, P, N or halogen (Cl, F, Bor '1) atom or atoms. 1 This application is a continuation-in-part ofthe following copending applications: M. T. Harvey, Ser. No. 605,207,filed August 20, 1956; Harvey et .al., Ser. No.

640,578, filed February 18, 1957, and Harvey et a1, Ser. 3 No. 772,177,filed November 6, 1958, all now abandoned. Examples of hydrogenatediurfural-ketone condensa- V tion products and methodsof makingfurf-ur-al-ketones and hydrogenation products are given in my US.Patents Nos. 2,600,403 and 2,600,764 issued June 17, 1952, to whichreference is hereby made as partof this disclosure.

The hydrogenation products of f-urfural ketones useful in the practiceof the present invention are describe 7 generally as those of thefollowing formulas:

in which R is a hydrocarbon or a carbohydrate radical. The termcarbohydrate radical as here used is considered 'to include hydrocarbonor carbohydrate radicals having one or more of the radicals =C 0 andHowever, alongwith compounds I, ll, Ill and IV there will be formedother compounds which represent various combinations and permutations ofhydrogenation at the three carbon to carbon double bonds and at thebutone of the compounds (I) to (IV), inclusive, will usually predominatein the reaction mass at any of the [four degrees of hydrogenationrepresented by said compounds represented by the formulas (l) to (IV).The R rep resents one of any radical of'one to twenty-two carbon atomseither in straight or branched chain with or Without radicals of ringcompounds thereon (such as one of the furan radicals, the phenyl radicalor the cyclic hexradical to either a =C=O radical or to a radical. Andduring hydrogenation steps to obtain one or more of said compounds (I)to (VI), when R contains an unsaturated carbon to carbon double bond, a=&O radical or a radical, hydrogenation in R can take place during orafter hydrogenation such as takes place in the illustrative generalExamples I to VI described above.

Specific examples of the furfural ketone compounds which whenhydrogenated are useful in the practice of the present invention are asfollows:

In the claims the hydrogenated furfural ketone com- 4 pounds used in thepractice of the present invention are represented generically by theformulas such as in which R is stated to be a hydrocarbon or acarbohydrate and for the purposes of this disclosure the termhydrocarbon is intended to cover radicals such as as exemplified in theabove examples.

HYDROGENATED 'FURFURAL KETONES :FAI-H FAHI, as made in accordance withthe disclosures inmy said US. Patents Nos. 2,600,403 and 2,600,764 anddistilled at C. at 5 mm. of Hg pressure contains about ten moles of:

Reference is also hereby made to my said U.S. Patent 2,600,764 for thedescription of a method of making monofurfural acetone:

and for the method of hydrogenating the latter compound to produce themonofurfuryl acetone which latter has the molecular weight of 138,boiling point of 75 C. at 1 mm. of mercury, specific gravity of 1,035,freezing point at -55 C., and is soluble in alcohols, ketones, benzeneand other aromatic solvents, organic esters, and cashew nut shell liquidand other phenols. As noted elsewhere, FAHI is soluble to the extent ofabout 1 part to about 8 parts of kerosene.

FAHI dissolves pyrethrum and other insecticidal pyrethrins, rotenone andother insecticidal rotenoids, DDT, 2,4-D and Lindane (the chemicalformulas for the latter three materials are given elsewhere herein).Rotenone is completely soluble in FAHI. DDT is soluble up to a 25%concentrate in FAHI.

FAHII When desired, the hydrogenated product FAHII:

Uaaiaaij FAHZ 4-(4,5 dihydro alpha furyD-Z-butanone.

This comt pound, herein called F-HAZ, has a specific gravity of plantswere placed on a rotating table to insure uniform 1.080 and analysis ofa first distillate from a hydrogenadeposit of material. Immediatelyafter spraying the plants tion reaction mass showed the presence ofabout2.7% were removed to a holding room maintained-atSO" F.

of the distillate as having --OH radical at the place of and a relativehumidity of 50%. Counts of living and the ketone radical originallypresent. This distillate was 5 dead mites were made under a binocularmicroscope. taken at 111 C. at about 18 mm. of mercury. Results ofphotomigration tests on mosquito larvae.- FAHI was tested atconcentrations ranging from to 1000 ppm. The active range in 1 hourtests was 300 to Mosquito Larvae ONE HOUR TEST 1 FM-HI 600 ppm. In 24hours l00.p.p.m. gave 44% moribund O 10 as compared with 97% for DDT at.0016 ppm.

H H ll H L J' 1 (CH3)I Table A.--Efiectiveness of FAHI on Photomigrationof monofurfuryl mesityil oxide. This compound, monofurfural mesityloxide when hydrogenated to the extent Compound V Concentw Percent of onecarbon-to-carbon double bond per molecule, distion p.p.m. moribund tillsat about 127 (C. at 15 mm. of mercury. i

' 100 81 FMEHI 3 0 l H2 1 2 ll 2 -CC-CCCHs t v 3; monoturfuryl methylethyl ketone. This compound, 0016 g monofurfural methyl ethyl ketonewhen hydrogenated 1 04 to the extent of one carbon-to-carbon double bondper 7 molecule, distills at about 106 C. at 15 mm. of mercury.

Table B ,EMIPHI I I ONE HOUR TEST 0 Compound C onccntra- Percent l H2 H2H H2 H2 H V t1onp.p.m. IDOI'llOIJI'ld CCCC-C-C(CH3)2 v 0 200 8 400 s3500 92 monofurfuryl methyl ISOPI'OPYl ketone. T his compound, 23% 8%monofurfural methyl isopropyl ketone when hydrogen- 800 100 ated to theextent of one carbon-to-carbon double bond Acet De 8 per molecule,distills at l051l5 C. at about 15 mm. of o '7 mercury.

FMIBHI Table C p ONE HOUR TEST 0 l LE2 H2 H .112 H Compound Oonoentra-Percent 0 CCACGC (011a): V tion p.p.m. moribund g 100 10 monofurfurylmethylisobutyl ketone. This compound, 388- i3 monofurfural methylisohutyl ketone when hydrogenated 288 3% to the extent of onecarbon-to-carbon double bond per 00 100 molecule, distills at about 130*at 15 mm. of merggg' lgg cury. 900 100 The effectiveness of FAHI,submitted for evaluation as 1,008 1 188 a possible insecticide, wasdetermined in tests for the con 1% y 0 trol of mosquito larvae andtwo-spotted mite. Insecticidal evaluations were made with thephotomigration method using Ae'des aegypti (l...) mosquito larvae- Thismethod has been perfected into a precision bioassayby taking Mosquito-Larvae advantage of the negative phototropic response of mos- ONE HOUTEST quito larvae.-

Having determined the insecticidal activity in ppm. Compound concentra-Percent on mosquito larvae, the material was then sprayed on mppmTendergreen bean plants infected with two-spotted mite,

' Tetranychus bimaculatus Harvey. Triton X-1 55 was 283 32 used as awetting agent. Parathion (0,0-diethyl-O-p- 3g nitrophenylthiophosphate), Diland (1 part of 1,l-bis(p- 800chlorophenyl)-2-nitropropane and 2 parts of l,l-bis (p- 021chlorophenyl)-2-nitrobutane) and Ovotran (p-ch-lorophenylp-chlorobenzene sulfonate) were used as standards. I

- The materials were sprayed with a De Vilbiss spray- Results of Testson Two-Spotted Mite.-It willbe-noted gun (Model CH 6-2041) adjusted tospray ml. in 30 in Table E that FAHI gave a kill of young and adult two-I seconds at a pressure of 40 lbs. per sq. in. The potted 75 spottedmite, Tetranychus bimaculazus Harvey of 83% Table D.Efiectiveness ofFAHI on Photomigration 0f at 500 p.p.m.,90% at 600 p.p.m. and 95% at1000 p.p.m. in 48 hours. This compares with Ovotran at 200 mg./100 ml.for the same period. FAHI also possesses ovicidal action as the killswere 88% at 300 p.p.m. and 93% at 600 p.p.m. and at 1000 p.p.m. at theend of 7 days. This compares with 91% kill for O'votran.

Table E.Efiectiveness of FAHI on Adult and Young of Two-Spotted Mite 48Hours After Spraying and Ovicia'al I Action at End of 7 Days PercentPercent N umkill cor- Numkill cor- Oompound Concentration her rected bcrrccted mites for blank mites for blank (48 hr. at end of count) 7 days50 mgJlOO ml 45 55 61 26 100 mg./100 ml 41 67 55 83 200 mg./100 ml 52 9060 91 1.0% 49 46 0 Titron X-155.

Oheck 49 0 43 0 44 73' 57 70 50 80 61 86 68 10 33 43 50 11 39 78 41 9053 93 51 1 59 15 43 0 54 0 39 3 71 56 43 83 54 88 41 90 51 93 43 95 5093v The following experiments were conducted with FAHI as a carrier andsynergist of pyrethins on the housefly, Musca domestica L. and as acarrier and sy-nergist of rotenone of the southern armyworm, Prodenz'aeridania (Cram) and the two-spotted mite, T etranychus bimaculatusHarvey.

LARGE GROUP FEET-GRADY TEST RESULTS FAHI appears to synergize pyrethins.There is no question as to the increased activity of pyrethrins in FAHIas compared with Deobase (Table 1).

In Table 2, results are shown for 100 mg. of pyrethrins in Deobase (1)and in a mixture containing 90 m1. of Deobase and 10 ml. of FAHI (2).Increased kill and knockdown are probably statistically significant for(2) over that of (1). Note high kill results for Test No. 1. Highervolumes of FAHI in Deohase were not tested as a solvent coupler would'be needed. About 10% by volume of FAHI seemed to 'be the maximumwithout separation of diluents. These tests suggest considerableactivity and interest for FAHI.

Table 1.-FAHI and Deobase Compared as Carriers for Pyrethrins by theLarge Group Peer-Grady Test Method Percent Percent knockdown Formulationkill for 24 hours 3 min. 5 min. min.

50 mg. pyrethrins in deobase:

Average 25.5 67.8 76.1 81.2

50 n1 ethrins in FAHI:

Table 2.-Large Group Peer-Grady Test Results Comparing PyrethrinsFormulated in Deobas and in a Combination of Deobase Plus FAHI PercentPercent knockdown Formulation kill for 24 hours 3 min. 5 min. 10 min.

100 mg. pyrethrins in 100 ml. deobase:

Average 29 .4 .3 90 .9 93 .7

100 mg. pyretlirins in 90 ml. deobase plus 10 ml FAHI- Average 39.7 93.3 95.9 96.7

O.T.I. (oflicial test insecticide):

Average 34 .1 87 .0 91 .2 94 .6

Table 3.-Results of Tests With Adult and Young of T wo- Spotted Mile 48Hours After Spraying and Ovicidal Action at End of 7 Days RESULTS OFTESTS ON TWO-SPOTTED MJTE In the \foregoing Table 3 potted bean plantswere sprayed with a solution consisting of FAHI 400 p.p.m. and rotenone,C1. 2500 p.p.m. 'Ilhis solution gave a kill of 87% in 48 hours to adultand young two-spotted mite and an ovicildal efiect in 7 days of 97%.This compared with Malathion(O,O-dimethyl-5-(1,2-1dicarboxyethyDdithiosulphate) at 40 p.p.m. whichgave a kill of 91% of adults and young and a 7-day oviciidal eifect of97%. (Eor method of spraying see Hantsell, A., Harry L. Haymes andDonald P. Connola, C.B.T.I. 15: 131-140, 1948.) RESULTS OF TESTS ONSOUTHERN ARMYWORM In making up solutions to be tested on the southernarmyworm ldirect quantities of FAHI, acetone and notenone (100% tech.)were added to water containing a.

lowed to dry at room temperature and placed in Petri.

dishes with two filter paper @1868 moistened with '1 ml. of Water. Fourlarvae were added to each dish and [the tests run in duplicate. Afterthe larvae had been in contact with the bean leaves for 72 hours, countsof percent of leaf consumed and'percent kill 'Were established. Theresults of these tests appear in Tables 4 and 5.

'Rotenone at a concentration of 4500 p.p.m. gave a kill of 38% and 90%protection of foliage. Rotenone at the same concentration and FAHI at1000 p.p.m. gave 50% kill and 85% protection of foliage. When 10 p.p.m.of FAHI was present in 5000' thnough 8000 p.p.m. of rotenone, percentkill was increased. Activity was also increased for rrotenone at 10,000p.p.m. when 100 ppm. of FAHI was presen As the concentration of FAHI wasincreased the protection of rioliage increased .up to concentrations or8000 ppm.

Table 4.Results of Southern Armyworm Tests Concen- Total PercentChemical 'tration number Percent bean leaf in ppm. larvae kill eatenRotenone, in acetone 4, 500 8 38 10 &8 s 25 35 s 15 4,500 1,000 s 50 15g 5,000 8 25 v 0.5 ig s as 10 s 25 0.5 2,00 '10 as 0.5

0 1:000 10 75 0.3 ggoo 1s 75 0.5

A second series of tests were conducted to determine at whatconcentration of rotenone could be prepared rising FAHI as a solvent(Table Stock solutions of 5% and in FAHI were made up. Rotenone wascompletely soluble in FAH-I at both concentrations while only completelysoluble in acetone at 5%. Increasing concentrations of FAHI (3% to 6%)were used with increasing concentrations of rotenone. Rotenone inacetone was superior to rotenone in 'FAI-ll in toxicity to the larvaebut toliage protection was FAHI was used as the solvent. 10%concentrates were tested and gave higher kills of larvae and increasedpro,- tection to bean foliage. A 3% concentration of FAHI also gavecomplete kill of larvae.

Table 5.Results of Southern Armyworm Tests 1 Figures in p.p.1n. refer toactive ingredient (rotenone); figures per cent refer to carrier FAHI oracetone.

MISCELLANEOUS OBSERVATIONS TEST RESULTS:

concentrate appeared temperature stable at [greater when one weekfollowing treatment. 1

TESTS FOR TOFGCITY OF HYDROGENATED FURFURAL-KETONES These materials,FAHI, FAHZ and FAHII were tested for oral toxicity, as follows:

Method: Adult, male, albino rats of the Sprague- Dawley strain weighingapproximately 200 g. were used for this work. The animals were housed inindividual,

screen bottom cages and provided with a commercial laboratory chow andwater ad libitum except that the rats were fasted overnight just priorto treatment. The samples were administered via stomach tube andgraduated syringe in calculated amounts, The animals were closelyobserved for evidences of Results:

Compound tested Dose Animals Animals (cc/kg.) treated killed Conclusion:Under the test, conditions outlined above, the samples have acute oralLD 50 values for the rat approximately as tabulated below:

" Approx. LD 50 (cc/kg.)

FAHI O 5 FAHII 1-10 FAHZ 10 It can be seen from a consideration of theabove that in the hydrogenated furfural-ketone products described, thegreater the'degree of hydrogenation the greater are both theinsecticidal value of the material and the synergistic value thereof andalso the lesser the degree of oral toxicity thereof. This is consideredto be an unexpected result, not shown or indicated by any known priorart.

While the products (3) have been generally exemplified by the particularcompounds (11) to (m) above, said compounds (a) to (m) are given not byway of limitations, it being considered that straight chain and branchedchain compounds are included in products (3) and that the branches canhave the furane-ketone relationship described hereinabove, forillustrative examples,

toxicity for a period of where R is a radical of the group and Xrepresents any of the radicals and wherein although all of the presentin the molecule.

The base (2) can be of various kinds, for example, the

mineral oil bases exemplified by deodorized kerosine;

emulsions containing soaps and soap solutions; and gases such asdichlorodifluoromethane and other halogenated carbon compounds such asare used for spray or mist application of liquid and finely divided dustproducts or of solid material in solution or suspension in a liquid, asin aerosol bombs and in airplane sprays.

An example of an emulsion which includes the material of the presentinvention is as follows:

20 parts by weight of oleic acid and 70 parts of a 5% solution of NaOHare heated together to form the sodium oleate to which 50 parts of amixture containing equal parts by weight of FAHZ (or FAHI) and ofcommercial insecticidal pyret hrin or of pyrethrin flowers in fine-dustform This mixture makes a homogeneous emulsion which can be used in theproportions set forth or can be diluted with an equal volume of water.

Any of the materials FAHII, FAHI, FMEHI, FMIPH-I or FMIBI can beused inplace of the FAHZ (or FAHI) in the above formula, and in place of thepyrethrin material, an equal amount of rotenone or of chlorinatedhydrocarbon can be used.

Reference is hereby made to Chemistry and Uses of Pesticides (1956'),Second Edition, E. R. de Ong, published by Reinhold Publishing Co., ofNew York, N.Y., for general formulations in Which the hydrogenatedfurfural-ketone reaction products of the present invention can be usedas synergist with the insecticidal materials, for illustrative example,in equal amounts by weight with the insecticidal material.

The examples given are illustrative and not limiting.

Two parts to five parts by weight of any of the hydro genatedfurfural-ketone products together with two parts to five parts of any ofthe pyrethrin, rotenone or halogenated hydrocarbons in about one hundredto two hundred parts of kerosene (Deobase for example) is an example ofthe use of a liquid base for the products of the present invention.

1 claim:

1. In an insecticidal composition, in combination (a) insecticidalmaterial selected from the group consisting of the pyrethrins, rotenonesand halogenated hydrocarl2 hens and (b) a synergist compound comprisinga completely saturated carbon chain having a terminal radical at eachend thereof, one of said terminal radicals being selected from the groupconsisting of the three rings:

and the other terminal radical being selected from the group consistingof the aforesaid three rings and alkyl, said carbon chain including as apart thereof intermediate said terminal radicals a radical selected fromthe group consisting of which intermediate radical is separated from theterminal radical when the terminal radical is one of the aforesaid threerings by the group -CH -CH forming a part of said carbon chain and whichintermediate radical is.

attached directly to the terminal radical when the terminal radical isthe said alkyl group.

2. An insecticidal composition as defined in claim 1, in which thehalogenated hydrocarbon is 2,2-bis-(p-chlorphenyl l, 1 l-trichlorethane.

3. An insecticidal composition as defined in claim 1,

in which the halogenated hydrocarbon is 2,4 dichlorophenoxy acetic acid.

4. An insecticidal composition as defined in claim 1, in which thehalogenated hydrocarbon is gamma isomer of hexachlorocyclohexane.

5. An insecticidal composition as defined in claim 1, in which thehalogenated hydrocarbon is dichlorodifluoromethane.

6. An insecticidal composition as defined in claim 1,

with (b) being '1 l L seats 0 Ha Hz in which R is an alkyl radical.

7. In an insecticidal composition, in combination (a) insecticidalmaterial selected from the group consisting of the pyrethrins,rotenones, and halogenated hydrocarbons and (b) a compound representedby XCORR Hz Hg in which X represents a radical selected from the groupconsisting of:

lot U U- R is a radical selected from the group consisting of and R isan alkyl radical.

8. In an insecticidal composition, in combination, (a) a pyrethrin and(b) a compound represented by in which X represents a radical selectedfrom the group consisting of:

and R represents a radical selected from the group consisting of it I Cand (IJHOH 13 14 9. In an insecticidal composition, in combination, (a)References Cited in the fileof this patent a pyrethrin and (b) acompound represented by UNITED STATES PATENTS X- R -CX E, 1%, E2 E2 72,146,258 Goodhue Feb. 7, 1939 in which each X represents a radicalselected from the 5 2,212,529 Swaine 27, 1940' group consisting of;Bartlett Ian. 9, l OTHER REFERENCES k and Drake: Abstract of applicationS.N. 70,382.

0 0 10 Stewart: Abstract of application S.N. 707,526. and R represents aradical selected from the group con- Edd JOUL ECQ B 47 1954 P. 501.sisting of

1. IN AN INSECTICIDAL COMPOSITION, IN COMBINATION (A) INSECTICIDALMATERIAL SELECTED FROM THE GROUP CONSISTING OF THE PYRETHRINS, ROTENONESAND HALOGENATED HYDROCARBONS AND (B) A SYNERGIST COMPOUND COMPRISING ACOMPLETELY SATURATED CARBON CHAIN HAVING A TERMINAL RADICAL AT EACH ENDTHEREOF, ONE OF SAID TERMINAL RADICALS BEING SELECTED FRON THE GROUPCONSISTING OF THRE THREE RINGS: